Reactive dyes containing fluoro-chloro-pyrimidyl groups and vinylsulfonyl groups or the like

ABSTRACT

Reactive dyes of the formula ##STR1## in which D is the radical of a dye of the monoazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimide series, R 1  is hydrogen or an unsubstituted or substituted C 1-4  -alkyl radical, and X is the vinyl, β-sulfatoethyl, β-thiosulfatoethyl, β-chloroethyl or β-acetoxyethyl group, are suitable in particular for dyeing and printing cellulose-containing fibre materials by the cold pad-batch method and produce, in high dyeing yields, dyeings and prints having good fastness properties.

This application is a continuation of now abandoned application Ser. No.873,437, filed Jun. 4, 1986, which application is in turn a continuationof now abandoned application Ser. No. 636,362, filed Jul. 30, 1984.

The present invention relates to novel reactive dyes, to a process fortheir preparation, and to their use for dyeings and printing fibrematerials.

The practice of dyeing with reactive dyes has in recent years led toincreased demands on the quality of the dyeing and the economics of thedyeing process There consequently continues to be a demand for newreactive dyes with improved properties, in particular applicationproperties.

The demand these days in the dyeing of cotton by the cold pad-batchmethod is for reactive dyes which are sufficiently substantive at thelow dyeing temperature and which also have good wash-off properties whenunfixed. They should also be highly reactive, so that only shortbatching times are required, and they should in particular producedyeings having high degrees of fixation. Existing dyes meet theserequirements only to an insufficient degree.

It is therefore the object of the present invention to provide new,improved reactive dyes for the cold pad-batch method which have thequalities characterised above to a high degree. The new dyes should bedistinguished especially by high degrees of fixation and high fibre-dyebond stabilities, and the unfixed portions on the fibre should moreoverbe readily washed off. They should also produce dyeings having goodall-round fastness properties, for example light- and wet-fastnessproperties.

This object is achieved with the novel bireactive dyes definedhereinafter.

The invention provides reactive dyes of the formula ##STR2## in which Dis the radical of a dye of the monoazo, metal complex azo,anthraquinone, phthalocyanine, formazan, azomethine, dioxazine,phenazine, stilbene, triphenylmethane, xanthene, thioxanthone,nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimideseries, R₁ is hydrogen or an unsubstituted or substituted C₁₋₄ -alkylradical, and X is a vinyl, β-sulfatoethyl, β-thiosulfatoethyl,β-chloroethyl or β-acetoxyethyl group.

The radical D in the formula (1) can be substituted in the customarymanner. Examples of further substituents on the radical D are alkylgroups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl,isopropyl or butyl, alkoxy groups having 1 to 4 carbon atoms, such asmethoxy, ethoxy, propoxy, isopropoxy or butoxy, acylamino groups having1 to 8 carbon atoms, such as acetylamino, propionylamino orbenzoylamino, amino, alkylamino having 1 to 4 carbon atoms, such asmethylamino, ethylamino, propylamino, isopropylamino or butylamino,phenylamino, N,N-di-β-hydroxyethylamino, N,N-di-β-sulfatoethylamino,sulfobenzylamino, N,N-disulfobenzylamino, alkoxycarbonyl having 1 to 4carbon atoms in the alkoxy radical, such as methoxycarbonyl orethoxycarbonyl, alkylsulfonyl having 1 to 4 carbon atoms, such asmethylsulfonyl or ethylsulfonyl, trifluoromethyl, nitro, cyano, halogen,such as fluorine, chlorine or bromine, carbamoyl, N-alkylcarbamoylhaving 1 to 4 carbon atoms in the alkyl radical, such asN-methylcarbamoyl or N-ethylcarbamoyl, sulfamoyl, N-alkylsulfamoylhaving 1 to 4 carbon atoms, such as N-methylsulfamoyl,N-propylsulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl,N-(β-hydroxy-ethyl)-sulfamoyl, N,N-di-(β -hydroxyethyl)-sulfamoyl,N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl and sulfo.The radical D preferably contains one or more sulfonic acid groups.Reactive dyes of the formula (1) in which D is the radical of an azo dyecontain as substituents especially methyl, ethyl, methoxy, ethoxy,acetylamino, benzoylamino, amino, chlorine, bromine, ureido, hydroxyl,carboxyl, sulfomethyl or sulfo.

An alkyl radical R₁ is straight-chain or branched; it can be furthersubstituted, for example by halogen, hydroxyl, cyano, C₁₋₄ -alkoxy,carboxyl or sulfo. Examples of R₁ are the radicals methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl,carboxymethyl, β-carboxyethyl, β-carboxypropyl, methoxycarbonylmethyl,ethoxycarbonylmethyl, β-methoxyethyl,β-ethoxyethyl, β-methoxypropyl,β-chloroethyl, γ-bromopropyl, β-hydroxyethyl, β-hydroxybutyl,β-cyanoethyl, sulfomethyl, β-sulfoethyl, aminosulfonylmethyl andβ-sulfatoethyl. R₁ is preferably hydrogen, methyl or ethyl.

Preferred reactive dyes have the formula (1) in which D is the radicalof a monoazo dye or of a corresponding metal complex azo dye. In thiscase the reactive radicals, i.e. the vinyl or β-sulfatoethyl etc.-sulfonyl radical and the 2,4-difluoro-5-chloropyrimidyl radical arebonded to different or identical radicals of starting components, namelydiazo and coupling components. The reactive dyes then for example havethe formula ##STR3## in which R₁ and X are as defined under the formula(1), D₁ is the radical of a diazo component, and K is the radical of acoupling component. If two X-SO₂ reactive radicals are present, they arebonded in particular to the radical of the diazo component; and in thecase where the dye molecule contains two 2,4-difluoro-5-chloropyrimidylradicals, these are preferably in the coupling component. Accordingly,depending on the indices attached to the reactive radicals in theformula (1), trireactive and tetrareactive dyes are also included. Theabove explanations also hold analogously for metal complex azo dyes.

Also included are reactive dyes of the formula (1) in which one of thereactive radicals or both are bonded to the chromophore via a radical ofthe formula ##STR4## the X-SO₂ - radical or the2,4-difluoro-5-chloropyrimidylamino radical being bonded to E; E is anunsubstituted or substituted aliphatic or aromatic bridge member. Thebridge member E is preferably an alkylene or arylene radical. Forinstance, E can be a long (for example of 10 or more carbon atoms) orshorter, straight-chain or branched alkylene radical; it can be inparticular an alkylene radical having 2 to 6 carbon atoms, for exampleethylene, propylene, butylene, hexylene or cyclohexylene. An aryleneradical E is for example a naphthylene radical, the radical of adiphenyl or of stilbene or in particular a phenylene radical. Theradical E can contain further substituents, for example halogen atoms,such as fluorine, chlorine and bromine, alkyl groups having 1 to 4carbon atoms, such as methyl, ethyl and propyl, alkoxy groups having 1to 4 carbon atoms, such as methoxy, ethoxy, propyloxy and isopropyloxy,carboxyl or sulfo. R and R', independently of each other, are eachhydrogen or an unsubstituted or substituted C₁₋₄ -alkyl radical; and Yis a halogen atom, a substituted or unsubstituted amino group, hydroxyl,or an alkoxy, aryloxy, alkylthio or arylthio group.

Preference is given to:

Reactive dyes of the formula ##STR5## in which R₂ is hydrogen, methyl orethyl, X is as defined under the formula (1), and the benzene ring A canbe further substituted;

reactive dyes of the formula ##STR6## in which X is as defined under theformula (1), and the benzene ring A can be further substituted; reactivedyes of the formula ##STR7## in which R₃ is hydrogen, methyl or ethyl, Xis as defined under the formula (1), and the benzene ring A can befurther substituted; and reactive dyes of the formula ##STR8## in whichX is as defined under the formula (1), and the benzene ring A can befurther substituted.

Preference is also given to reactive dyes of the formulae (2) to (5) inwhich the benzene rings A are not further substituted and/or in which Xis the vinyl or β-sulfatoethyl group.

The process for preparing the reactive dyes of the formula (1) comprisesreacting dyes of the formula ##STR9## in which D, R₁ and X are asdefined under the formula (1), or their precursors, with2,4,6-trifluoro-5-chloropyrimidine to reactive dyes of the formula (1),or converting the resulting intermediates into the desired end dyes, andif desired subsequently carrying out a further conversion reaction.

The starting materials are thus dyes which already contain an X-SO₂ -group, and the -N(R₁)H group is acylated with2,4,6-trifluoro-5-chloropyrimidine; or use is made of correspondingprecursors, for example a diazo component of the formula ##STR10## andthese precursors are coupled onto a coupling component which contains an--N(R₁)H group and the --N(R₁)H group is acylated before or after thecoupling with 2,4,6-trifluoro-5-chloropyrimidine. In the embodimentdescribed above, the acylatable --N(R₁)H group can also be present inthe diazo component, and the X-SO₂ - group correspondingly in thecoupling component. The diazo components used in this case areespecially 1,3-phenylenediamine-4-sulfonic acid,1,4-phenyl-enediamine-2-sulfonic acid,1,4-phenylenediamine-2,5-disulfonic acid or1,3-phenylenediamine-4,6-disulfonic acid. If desired use is made ofcorresponding acetylamino and nitro compounds in which the acetylaminoand nitro groups respectively are converted into the H₂ N group byhydrolysis and reduction respectively before the condensation with2,4,6-trifluoro-5-chloropyrimidine. The position of the reactiveradicals in the finished azo dye is thus not inflexibly tied to certainstarting components - diazo or coupling components.

The two reactive radicals can also be bonded to one and the samecomponent, for example by using a non-fibre-reactive diazo component anda coupling component of the formula ##STR11## and acylating the --NH₂group after the coupling with 2,4,6-trifluoro-5-chloropyrimidine.

The process variant where the starting materials are dye precursors issuitable for preparing reactive dyes of the formula (1) in which D isthe radical of a dye composed of two or more components. Examples ofsuch dyes composed of two or more components are monoazo, metal complexazo, formazan and azomethine dyes. The reactions involved in preparingthe end dyes from precursors are usually couplings leading to azo dyes.

In principle, the reactive dyes of the formula (1) of all dye classescan be prepared in a manner known per se or analogously to knownprocedures by starting from precursors or intermediates for dyescontaining fibre-reactive radicals according to the formula (1) orintroducing these fibre-reactive radicals into intermediates of dyecharacter which are suitable for this purpose.

Another advantageous method comprises first of all preparing a dye whichcontains a precursor of the reactive radical and subsequently convertingthis precursor into the end stage, for example by esterification or anaddition reaction. For example, it is possible to prepare a dye of theformula (6) in which X is a HO-CH₂ CH₂ - radical and to react theintermediate with sulfuric acid before or after the acylation, so thatthe hydroxyl group is converted into the sulfato group; or to use ananalogous dye in which X is the vinyl group, H₂ C═CH--, and to addthiosulfuric acid onto the intermediate, forming a HO₃ SS--CH₂ CH₂-radical. The sulfation of the hydroxyl group in a dye of the formula(4) or a suitable precursor is effected for example by reaction at 0° C.to moderately elevated temperatures with concentrated sulfuric acid. Thesulfation can also be effected by reacting the hydroxy compound with 2equivalents of chlorosulfonic acid per hydroxyl group at 10 to 80° C. ina polar organic solvent, for example N-methylpyrrolidone. The sulfationis preferably effected by adding the compound in question attemperatures between 5° and 15° C. to sulfuric acid monohydrate. Theintroduction into a compound of the formula (1) or an intermediate, of aradical detachable under alkaline conditions, for X other than thesulfato group, for example a thiosulfato group, is effected in a mannerknown per se.

Moreover, elimination reactions can be carried out subsequently to thesynthesis. For example, the reactive dyes of the formula (1) whichcontain sulfatoethylsulfonyl radicals can be treated withacid-eliminating agents, such as sodium hydroxide, and thesulfatoethylsulfonyl radicals turn into vinylsulfonyl radicals.

In many cases the method of preparation described above, namely via anintermediate of the reactive radical, has just a single product and goesto completion.

If groups capable of metal complex formation are present in the reactivedyes prepared, the reactive dyes can also be subsequently metallised.

As the individual steps of the process given above can be carried out indifferent orders, there are various possible process variants. Ingeneral the reaction is carried out in successive steps, the order ofthe elementary reactions between the individual reactants advantageouslybeing arranged in accordance with the particular conditions. Ashydrolysis of the 2,4-difluoro-5-chloropyrimidyl radical can occur undercertain conditions, an intermediate which contains acetylamino groupshas to be hydrolysed (to split off the acetyl groups) before thecondensation with 2,4,6-trifluoro-5-chloropyrimidine. Which part of theoverall reaction is advantageously carried out first varies from case tocase and is arranged especially according to the solubility of the aminocompounds involved and the basicity of the amino groups to be acylated.The acylation of the dyes of the formula (6) or the dye precursors with2,4,6-tri-fluoro-5-chloropyrimidine is effected by methods known per se,preferably in aqueous solutions or suspensions and in the presence ofalkaline acid-binding agents, for example aqueous alkali metalhydroxides, carbonates or bicarbonates.

The most important process variants are reflected in the illustrativeembodiments.

There now follow specific examples of possible starting materials whichcan be used for preparing the reactive dyes of the formula (1).

The dyes of the formula (6) can be in particular dyes of the followingstructural types: ##STR12##

If, in preparing the preferred reactive dyes of the formula (1) in whichD is the radical of an azo dye, the starting materials are not finishedamino dyes, for example are not those described above, but are dyeprecursors, i.e. diazo and coupling components, one of the twocomponents has to have at least one acylatable amino group and the otherat least one X-SO₂ - group. Possible diazo components are in the mainsuitable compounds of the aminobenzene and aminonaphthalene series, forexample those contained in the azo dyes of the formulae given above,such as 1,3-diaminobenzene, 1,4-diaminobenzene,1,3-diamino-4-chlorobenzene, 1,3-diamino-4-methylbenzene,1,3-diamino-4-ethylbenzene, 1,3-diamino-4-methoxybenzene,1,3-diamino-4-ethoxybenzene, 1,4-diamino-2-methylbenzene,1,4-diamino-2-methoxybenzene, 1,4-diamino-2-ethoxybenzene,1,4-diamino-2-chlorobenzene, 1,4-diamino-2,5-dimethylbenzene,1,4-diamino-2,5-diethylbenzene, 1,4-diamino-2-methyl-5-methoxybenzene,1,4-diamino-2,5-dimethoxybenzene, 1,4-diamino-2,5-diethoxybenzene,2,6-diaminonaphthalene, 1,3-diamino-2,4,6-trimethylbenzene,1,4-diamino-2,3,5,6-tetramethylbenzene, 1,3-diamino-4-nitrobenzene, 4,4'-diaminostilbene, 4,4'-diaminodiphenylmethane, 4,4'-diaminobiphenyl(benzidine), 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine,3,3'-dichlorobenzidine, 3,3'-dicarboxybenzidine,3,3'-dicarboxymethoxybenzidine, 2,2'-dimethylbenzidine,4,2'-diaminodiphenyl (diphenyline),2,6-diaminonaphthalene-4,8-disulfonic acid,1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2,5-disulfonicacid, 1,4-diaminobenzene-2,6-disulfonic acid,1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonicacid, 1,4-diamino-2-chlorobenzene-5-sulfonic acid,1,4-diamino-2-methylbenzene-5-sulfonic acid,1,5-diamino-6-methylbenzene-3-sulfonic acid,1,3-diamino-6-methylbenzene-4-sulfonic acid, 3-(3'- or4'-aminobenzoyl-amino)-1-aminobenzene-6-sulfonic acid,1-(4'-aminobenzoyl-amino)-4-aminobenzene-2,5-disulfonic acid,1,4-diaminobenzene-2-carboxylic acid, 1,3-diaminobenzene-4-carboxylicacid, 1,2-diaminobenzene-4-carboxylic acid,1,3-diaminobenzene-5-carboxylic acid, 1,4-diamino-2-methylbenzene,4,4'-diaminodiphenyl oxide, 4,4'-diaminodiphenylurea-2,2'-disulfonicacid, 4,4'-diaminodiphenyloxyethan-2,2'-disulfonic acid,4,4'-diaminostilbene-2,2'-disulfonic acid,4,4'-diaminodiphenylethane-2,2'-disulfonic acid,2-amino5-aminomethylnaphthalene-1-sulfonic acid,2-amino-5-amino-methylnaphthalene-1,7-disulfonic acid,1-amino-4-methoxy5-aminomethylbenzene-6-sulfonic acid and1,3,5-triaminobenzene.

Examples of aromatic amines which can serve as diazo components inpreparing the monoazo or disazo dyes and which contain one or two bondedgroups of the formula X-SO₂ - are:

1-Amino-4-β-sulfatoethylsulfonylbenzene,1-amino4-β-thiosulfatoethylsulfonylbenzene,1-amino-4-vinylsulfonylbenzene, 1-amino-4-β-chloroethylsulfonylbenzene,1-amino-3-β-sulfatoethylsulfonylbenzene, 1-amino-3-vinylsulfonylbenzene,1-amino-2-methoxy-5-β-sulfatoethylsulfonylbenzene,1-amino-2-methoxy-5β-thiosulfatoethylsulfonylbenzene,1-amino-2-methoxy-5-vinylsulfonylbenzene,1-amino-4-methoxy-3-β-sulfatoethylsulfonylbenzene,1-amino-4-methoxy3-β-vinylsulfonylbenzene,1-amino-2,5-dimethoxy-4-β-sulfatoethylsulfonylbenzene,1-amino-2,5-dimethoxy-4-vinylsulfonylbenzene,1-amino-2-methoxy-4-β-sulfatoethylsulfonyl-5-methylbenzene,1-amino-2-methoxy-4-vinylsulfonyl-5-methylbenzene,1-amino-3-β-sulfatoethylsulfonyl-6-carboxybenzene,1-amino-3-vinylsulfonyl-6-carboxybenzene,1-amino-4-sulfatoethylsulfonylbenzene-2-sulfonic acid,1-amino-4-vinyl-sulfonylbenzene-2-sulfonic acid,1-amino-5-vinylsulfonylbenzene-2,4-disulfonic acid,1-amino-2-hydroxy-5-β-sulfatoethylsulfonylbenzene,1-amino-2-hydroxy-4-β-sulfatoethylsulfonylbenzene,1-amino-2-hydroxy-5-β-sulfatoethylsulfonyl-benzene-3-sulfonic acid,1-amino-2-bromo-4-β-sulfatoethylsulfonylbenzene,1-amino-2,6-dichloro-4-β-sulfatoethylsulfonylbenzene,1-amino-2,4-di-(β-sulfatoethylsulfonyl)-benzene, 1-amino-2,4-di-(β-sulfatoethylsulfonyl)-5-chlorobenzene, benzene,1-amino-2,4-di-(vinylsulfonyl)-benzene,1-amino2,4-di-(vinylsulfonyl)-5-chlorobenzene,1-amino-2,4-di-(β-acetoxyethylsulfonyl)-benzene,1-amino-2,4-di-(β-acetoxyethylsulfonyl)-5-chlorobenzene,2-amino-8-β-sulfatoethylsulfonylnaphthalene,2-amino-6-β-sulfatoethylsulfonylnaphthalene,2-amino-6-β-sulfatoethylsulfonylnaphthalene-1-sulfonic acid,2-amino-8-β-sulfatoethylsulfonylnaphthalene-6sulfonic acid and2-amino-6,8-di-(β-sulfatoethylsulfonyl)naphthalene.

A mention should also go to the corresponding β-hydroxy compounds whichcan be used as precursors, examples being1-amino-4-β-hydroxyethylsulfonylbenzene,1-amino-3-β-hydroxyethylsulfonylbenzene,1-amino-2,4-di-(β-hydroxy-ethylsulfonyl)-benzene and1-amino-2,4-di-(β-hydroxyethyl-sulfonyl)-5-chlorobenzene.

If the diazo component to be used is not a diamine but is anaminoacetylamino compound from which the acetyl group is subsequently tobe reeliminated by hydrolysis, as mentioned above in the description ofthe process, the monoacetyl compounds of the abovementioned diazocomponents are possible, examples being1-acetylamino-3-aminobenzene-4-sulfonic acid and1-acetylamino-4-aminobenzene-3-sulfonic acid.

The coupling components are chiefly suitable compounds of theaminobenzene and naphthalene series, for example anilines,N-monosubstituted anilines, m-phenylenediamine derivatives,aminonaphthalenes, naphthols, aminonaphthalenesulfonic acid,naphtholsulfonic acids or aminonaphtholsulfonic acids and alsopyrazolones, aminopyrazoles, aminopyridines, hydroxypyridines/pyridones,aminopyrimidines, hydroxypyrimidines, indoles, barbituric acidderivatives or acetoacetarylides. Examples are 1-amino-3-methylbenzene,1-amino-2-methoxy-5-methylbenzene, 1-amino-2,5-dimethylbenzene,3-aminophenylurea, 1-amino-3-acetylaminobenzene,1-amino-3-hydroxyacetylaminobenzene, 1,3-diamino-benzene-4-sulfonicacid, 1-aminonaphthalene-6- or -8-sulfonic acid,1-amino-2-methoxynaphthalene-6-sulfonic acid,2-aminonaphthalene-5,7-disulfonic acid,1-amino-8-hydroxy-naphthalene-6-sulfonic acid,1-amino-8-hydroxynaphthalene-2,4-disulfonic acid,2-hydroxy-3-aminonaphthalene-5,7-disulfonic acid,1-amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid,2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-methyl- or2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid,2-amino-5-hydroxynaphthalene-1,7-disulfonic acid,2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-methyl- or2-ethyl-amino-8-hydroxynaphthalene-6-sulfonic acid,2-amino-8-hydroxynaphthalene-3,6-disulfonic acid,1-amino-5-hydroxy-naphthalene-7-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid,1-(4'-aminobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulfonicacid, 2-(4'-amino-3'-sulfophenylamino)-5-hydroxynaphthalene-7-sulfonicacid, 1-amino-8-hydroxynaphthalene-4-sulfonic acid,2,4,6-triamino-3-cyanopyridine,1-β-aminoethyl-3-cyano-4-methyl-6-hydroxypyrid-2-one1-γ-aminopropyl-3-sulfomethyl-4-methyl-6-hydroxypyrid-2-one,1,3-diaminobenzene, 1-amino-3-(N,N-di-β-hydroxyethylamino)-benzene,1-amino-3-(N,N-di-β-sulfatoethylamino)-benzene, 1-amino-3-(N,N-di-β-hydroxyethyl-amino)-4-methoxybenzene,1-amino-3-(N,N-di-β-sulfatoethyl-amino)-4-methoxybenzene,1-amino-3-sulfobenzylaminobenzene,1-amino-3-sulfo-benzylamino-4-chlorobenzene,1-amino-3-(N,N-di-sulfo-benzylamino)-benzene,1-(3'-aminophenyl)3-methyl-5-pyrazolone as well as1-(aminophenyl)-3-carboxy-5-pyrazolones which can be substituted in thephenyl nucleus by chlorine, methyl, methoxy, nitro or sulfo, such as1-(2'-sulfo-4'-aminophenyl)-3-carboxypyrazol-5-one.

If one of the two components contains both reactive groups at the sametime or these can be introduced into the component in question, as inthe case of the coupling components of the formulae ##STR13## the othercomponent, in this case the diazo component, can also be non-reactive.Examples are aminobenzene, 1-amino-2-, -3- or -4-methylbenzene,1-amino-2-, -3- or -4-methoxybenzene, 1-amino-2-, -3- or-4-chlorobenzene, 1-amino-2,5-dichlorobenzene,1-amino-2,5-dimethylbenzene, 1-amino-3-methyl-6-methoxybenzene,1-amino-2-methoxy-4-nitrobenzene, 1-aminobiphenyl, 2-aminodiphenylether, 1-aminobenzene-2-, -3- or -4-sulfonamide, 1-aminobenzene-2-, -3-or -4-carboxylic acid, dehydrothio-p-toluidine-sulfonic acid,1-amino-3-trifluoromethylbenzene-6-sulfonic acid, 1-amino-benzene-2-,-3- or -4-sulfonic acid, 1-aminobenzene-2,4-and -2,5-disulfonic acid,1-amino-4-methylbenzene-2-sulfonic acid,1-amino-3-methylbenzene-6-sulfonic acid, 1-amino-6-methylbenzene-3- or-4-sulfonic acid, 1-amino-2-carboxybenzene-4-sulfonic acid,1-amino-4-carboxybenzene2-sulfonic acid, 1-amino-4- or-5-chlorobenzene-2-sulfonic acid, 1-amino-6-chlorobenzene-3- or-4-sulfonic acid, 1-amino-3,4-dichlorobenzene-6-sulfonic acid,1-amino-2,5-dichlorobenzene-6-sulfonic acid,1-amino-2,5-dichlorobenzene-4-sulfonic acid,1-amino-4-methyl-5-chlorobenzene-2sulfonic acid,1-amino-5-methyl-4-chlorobenzene-2-sulfonic acid, 1-amino-4- or-5-methoxybenzene-2-sulfonic acid, 1-amino-6-methoxybenzene-3- or-4-sulfonic acid, 1-amino-6-ethoxybenzene-3- or -4-sulfonic acid,1-amino-2,4-dimethoxy-benzene-6-sulfonic acid,1-amino-2,5-dimethoxybenzene-6-sulfonic acid,1-amino-2,5-dimethoxybenzene-4-sulfonic acid,1-amino-3-acetylaminobenzene-6-sulfonic acid,1-amino-4-acetylaminobenzene-2-sulfonic acid,1-amino-3-acetylamino-4-methylbenzene-6-sulfonic acid,2-amino-1-methylbenzene-3,5-disulfonic acid,1-amino-4-methoxybenzene-2,5-disulfonic acid, 1-amino-3- or-4-nitrobenzene-6-sulfonic acid, 1-aminonaphthalene, 2-aminonaphthalene,1-aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulfonic acid,2-aminonaphthalene-1-, -3-, -4-, -5-, - 6-, -7- or -8-sulfonic acid,2-aminonaphthalene-3,6- or -5,7-disulfonic acid,1-amino-naphthalene-3,6- or -5,7-disulfonic acid, 2-aminonaphthalene-1,5-, -1,7-, -3,6-, -5,7-, -4,8- or -6,8-disulfonicacid, 1-aminonaphthalene-2,5,7-trisulfonic acid,2-aminonaphthalene-1,5,7-, -3,6,8- or -4,6,8-trisulfonic acid,1-hydroxy-2-aminobenzene-4-sulfonic acid,1-hydroxy-2-amino-benzene-5-sulfonic acid,1-hydroxy-2-aminobenzene-5-sulfonic acid,1-hydroxy-2-aminobenzene-4,6-disulfonic acid,1-hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic acid,1-hydroxy-2-amino-o-acetylaminobenzene-4-sulfonic acid, 1-hydroxy-2-amino-4-chlorobenzene-5-sulfonic acid,1-hydroxy-2-amino-4-methylsulfonylbenzene, 1-amino-2-hydroxy-6-nitro-naphthalene-6-sulfonic acid, 2-amino-1-hydroxynaphthalene-4,8-disulfonicacid, 4-aminoazobenzene-3,4'-disulfonic acid,3-methoxy-4-amino-6-methylazobenzene-2',4'-disulfonic acid and3-methoxy-4-amino-6-methylazobenzene-2',5'-disulfonic acid.

The diazotisation of the intermediates containing a diazotisable aminogroup is generally effected at low temperatures by the action of nitrousacid in aqueous mineral acid solutions, coupling taking place at weaklyacid, neutral or weakly alkaline pH.

The condensation of 2,4,6-trifluoro-5-chloropyrimidine with the diazocomponents or the coupling components or with acylatable monoazointermediates or with the aminocontaining dyes of the formula (6) ortheir precursors preferably takes place at low temperatures and weaklyacid, neutral or weakly alkaline pH in aqueous solutions or suspensions.The hydrogen fluoride set free during the condensation is advantageouslycontinuously neutralised by adding aqueous alkali metal hydroxides,carbonates or bicarbonates.

The reactive dyes of the formula (1) are fibre-reactive. Fibre-reactivecompounds are to be understood as meaning those capable of reacting withthe hydroxyl groups of cellulose or with amino groups of natural orsynthetic polyamides to form covalent chemical bonds.

The reactive dyes of the formula (1) are suitable for dyeing andprinting a very wide variety of different materials, such as silk,leather, wool, nylon fibres and polyurethanes, and in particularcellulose-containing fibre materials of any kind. Examples of such fibrematerials are the natural cellulose fibre, such as cotton, linen andhemp, as well as pulp and regenerated cellulose. The reactive dyes ofthe formula (1) are also suitable for dyeing or printinghydroxyl-containing fibres contained in blend fabrics, for exampleblends of cotton with polyester fibres or nylon fibres.

The dyes according to the invention can be applied to the fibre materialand fixed on the fibre in various ways, in particular in the form ofaqueous dye solutions and print pastes. They are suitable not only forthe exhaust method of dyeing but also for dyeing by the pad-dyeingmethod whereby the cloth is impregnated with aqueous dye solutions whichcan, if desired, also contain salt, and the dyes are fixed, if desiredunder heat, after a treatment with alkali or in the presence of alkali.They are particularly suitable for the so-called cold pad-batch methodwhereby the dye is applied on a pad-mangle together with the alkali.After the fixing the dyeings or prints are thoroughly rinsed with coldand hot water which can, if desired, also contain an agent acting like adispersant and promoting the diffusion of the unfixed portions.

The reactive dyes of the formula (1) are distinguished by highreactivity and good fixing properties. They can therefore be used inexhaust dyeing at low dye temperatures and require only short steamingtimes in the pad-steam process. The degrees of fixation are high, andthe unfixed portions are readily washed off, the difference between thedegree of exhaustion and the degree of fixation being remarkably small,i.e. the hydrolysis loss being very low. The reactive dyes of theformula (1) are also suitable for printing, especially on cotton, butalso for printing nitrogen-containing fibres, for example wool, silk orwool-containing blend fabrics.

The dyeings and prints prepared with the dyes according to the inventionare distinguished by bright shades. In particular the dyeings and printson cellulose fibre materials are of high tinctorial strength and have ahigh fibre-dye bond stability not only in the acid but also in thealkaline range, and also good lightfastness and very good wetfastnessproperties, such as wash, water, sea water, cross-dyeing andperspiration fastness properties, as well as a good fastness topleating, hot-press fastness and rub fastness.

The following examples serve to illustrate the invention. Thetemperatures are given in degrees centigrade. The parts and percentagesare by weight, unless otherwise stated. Parts by weight relate to partsby volume as the kilogramme relates to the litre.

The preparation of the monoazo intermediates has not been described inall cases in the following illustrative embodiments, but it is anyhowreadily apparent from the general description.

EXAMPLE 1

64 parts of 1-amino-8-naphthol-3,6-disulfonic acid are dissolved at pH9.0-9.5 in 800 parts of water in the presence of 30% strength sodiumhydroxide solution. The solution is cooled down to 10° C., and 34 partsof 2,4,6-trifluoro-5-chloropyrimidine are added dropwise while pH9.25-9.5 is maintained by the dropwise addition of 5N sodium hydroxidesolution. The mixture is stirred at pH 8.5-9.0 at 15° C. for 15 minutesand is then brought to pH 6.5 by adding 4N hydrochloric acid solution.

The solution is used as a coupling component in dye synthesis.

To prepare the diazonium compound, 56 parts of aniline 4-β-sulfatoethylsulfone are suspended in 500 parts of ice-water, and the suspension isacidified with 45 parts of concentrated aqueous hydrochloric acid and isdiazotised with 40 parts by volume of 5N sodium nitrite solution. Themixture is stirred at about 5° C. for 2 hours and the excess nitrousacid is then destroyed by means of sulfamic acid. The diazonium saltsolution thus prepared is slowly added at pH 5.5-6.0 to the solution ofthe coupling component. The mixture is stirred for 2 hours until thecoupling has ended. pH 5.5-6.0 is maintained by adding sodiumbicarbonate. The dye is then precipitated with sodium chloride, isisolated using a suction funnel and is dried at 40° C. in vacuo.Grinding produces a red electrolyte-containing dye powder which containsthe sodium salt of the compound of the formula ##STR14##

This compound has very good dye properties and dyes cellulose materialsby the dyeing and printing methods customary for reactive dyes in bluishred shades having very good wetfastness properties.

EXAMPLE 2

64 parts of 1-amino-8-naphthol-3,6-disulfonic acid are dissolved at pH9.0-9.5 in 800 parts of water in the presence of 30% strength sodiumhydroxide solution. The solution is cooled down to 10° C., and 34 partsof 2,4,6- trifluoro-5-chloropyrimidine are added dropwise while pH9.25-9.5 is maintained by the dropwise addition of 5N sodium hydroxidesolution. The mixture is stirred at pH 8.5-9.0 at 15° C. for 15 minutesand is then brought to pH 6.5 by adding 4N hydrochloric acid solution.

The solution is used as a coupling component in dye synthesis.

To prepare the diazonium compound, 56 parts of aniline 3-β-sulfatoethylsulfone are suspended in 500 parts of ice-water, and the suspension isacidified with 45 parts of concentrated aqueous hydrochloric acid and isdiazotised with 40 parts by volume of 5N sodium nitrite solution. Themixture is stirred at about 5° C. for 2 hours and the excess nitrousacid is then destroyed by means of sulfamic acid. The diazonium saltsolution thus prepared is slowly added at pH 5.5-6.0 to the solution ofthe coupling component. The mixture is stirred for 2 hours until thecoupling has ended. pH 5.5-6.0 is maintained by adding sodiumbicarbonate. The dye is then precipitated with sodium chloride, isisolated using a suction funnel and is dried at 40° C. in vacuo.Grinding produces a red electrolyte-containing dye powder which containsthe sodium salt of the compound of the formula ##STR15##

This compound has very good dye properties and dyes cellulose materialsby the dyeing and printing methods customary for reactive dyes in bluishred shades having very good wetfastness properties.

EXAMPLE 3

64 parts of 1-amino-8-naphthol-4,6-disulfonic acid are dissolved at pH9.0-9.5 in 800 parts of water in the presence of 30% strength sodiumhydroxide solution. The solution is cooled down to 10° C., and 34 partsof 2,4,6-trifluoro-5-chloropyrimidine are added dropwise while pH9.25-9.5 is maintained by the dropwise addition of 5N sodium hydroxidesolution. The mixture is stirred at pH 8.5-9.0 at 15° C. for 15 minutesand is then brought to pH 6.5 by adding 4N hydrochloric acid solution.

The solution is used as a coupling component in dye synthesis.

To prepare the diazonium compound, 56 parts of aniline 4-β-sulfatoethylsulfone are suspended in 500 parts of ice-water, and the suspension isacidified with 45 parts of concentrated aqueous hydrochloric acid and isdiazotised with 40 parts by volume of 5N sodium nitrite solution. Themixture is stirred at about 5° C. for 2 hours and the excess nitrousacid is then destroyed by means of sulfamic acid. The diazonium saltsolution thus prepared is slowly added at pH 5.5-6.0 to the solution ofthe coupling component. The mixture is stirred for 2 hours until thecoupling has ended. pH 5.5-6.0 is maintained by adding sodiumbicarbonate. The dye is then precipitated with sodium chloride, isisolated using a suction funnel and is dried at 40° C. in vacuo.Grinding produces a red electrolyte-containing dye powder which containsthe sodium salt of the compound of the formula ##STR16##

This compound has very good dye properties and dyes cellulose materialsby the dyeing and printing methods customary for reactive dyes inneutral red shades having very good wetfastness properties.

EXAMPLE 4

48 parts of 2-amino-5-naphthol-7-sulfonic acid are dissolved at pH6.0-6.5 in 800 parts of water in the presence of 30% strength sodiumhydroxide solution. The solution is cooled down to 10° C., and 34 partsof 2,4,6-tri-fluoro-5-chloropyrimidine are added dropwise while pH6.0-6.5 is maintained by the dropwise addition of 5N sodium hydroxidesolution. The mixture is stirred at pH 6.0-6.5 at 15° C. for 20 minutes.

The solution is used as a coupling component in dye synthesis.

To prepare the diazonium compound, 56 parts of aniline 4-β-sulfatoethylsulfone are suspended in 500 parts of ice-water, and the suspension isacidified with 45 parts of concentrated aqueous hydrochloric acid and isdiazotised with 40 parts by volume of 5N sodium nitrite solution. Themixture is stirred at about 5° C. for 2 hours and the excess nitrousacid is then destroyed by means of sulfamic acid. The diazonium saltsolution thus prepared is slowly added at pH 5.5-6.0 to the solution ofthe coupling component. The mixture is stirred for 2 hours until thecoupling has ended. pH 5.5-6.0 is maintained by adding sodiumbicarbonate. The dye is then precipitated with sodium chloride, isisolated using a suction funnel and is dried at 40° C. in vacuo.Grinding produces a red electrolyte-containing dye powder which containsthe sodium salt of the compound of the formula ##STR17##

This compound has very good dye properties and dyes cellulose materialsby the dyeing and printing methods customary for reactive dyes in orangeshades having very good wetfastness properties.

EXAMPLE 5

281 parts of 4-β-sulfatoethylsulfonylaniline are added to 1000 parts ofwater and are dissolved therein by carefully adding 65 parts of sodiumcarbonate, pH 6.5-7.0 becoming established. The solution is stirred atthis pH for 2 hours, when 750 parts of ice and 255 parts of 31% strengthaqueous hydrochloric acid are added; 173 parts of 40% strength aqueoussodium nitrite solution are then added, the mixture is stirred at 0° to5° C. for a further 2 hours, and excess nitrous acid is then destroyedby means of sulfamic acid. To the diazonium salt suspension thusprepared is then added at pH 6.0-6.5, simultaneously with about 70 partsof sodium carbonate, a solution of the condensation product of 1 moleach of cyanuric chloride and 1-amino-8-naphthol-3,6-disulfonic acid and3-aminoacetanilide-4-sulfonic acid and2,4,6-trifluoro-5-chloropyrimidine. This solution of the condensationproduct is prepared as follows: 319 parts of1-amino-8-naphthol-3,6-disulfonic acid are added with stirring to amixture of 500 parts of water and 121 parts of 33% strength sodiumhydroxide solution; the solution should afterwards be at pH 6.5-7.0.This solution is added in the course of an hour at pH 3.0-3.8 to asuspension of 194 parts of cyanuric chloride, 800 parts of water and 800parts of ice. The mixture is then stirred at 0° to 5° C. and theindicated pH, maintained by sprinkling in 92 parts of sodiumbicarbonate, for a further hour. To this clear solution thus obtained isthen added 221 parts of 3-aminoacetanilide-4-sulfonic acid, followed by105 parts of sodium carbonate in the course of an hour during which thepH rises to 4.5-5.0. The solution is stirred at this pH for a further 2hours during which the temperature is maintained at 35° to 40° C. 400parts of concentrated sodium hydroxide are added, and the mixture isstirred at 70° to 75° C. for 2 hours. It is then neutralised withconcentrated hydrochloric acid. To this neutral solution is then addeddropwise in the course of an hour at 10° to 15° C. 169 parts of2,4,6-trifluoro-5-chloropyrimidine.

After the diazonium suspension and the solution of the couplingcomponent have been combined, the coupling mixture is stirred at roomtemperature for 2 hours during which it is held at pH 6.0-6.5 bysprinkling in 70 parts of sodium carbonate a little at a time. After thecoupling has ended the mixture is heated to 50° C., 40 parts ofkieselguhr are added, the solution is clarified by filtering, and thefiltrate is spray-dried.

The result is a red electrolyte-containing powder which contains thealkali metal salt, in particular the sodium salt, of the compound of theformula ##STR18## and may contain the buffer substance mentioned. Thiscompound has very good dye properties; it dyes the materials mentionedin the description, in particular wool from an acid bath or cellulosefibre materials in the presence of acid-binding agents, by theindustrially customary application and fixing methods for fibre-reactivedyes in clear red shades having very good build-up and a high degree offixation. The dyeings have very good wetfastness properties, for examplean excellent wash fastness, and a high resistance to steaming and verygood rub fastness, as well as very fast properties as regards thebleeding onto or staining of adjacent fabric.

EXAMPLE 6

64 parts of 1-amino-8-naphthol-3,6-disulfonic acid are dissolved at pH4.5-5.0 in 800 parts of water in the presence of 15 parts of sodiumcarbonate. The solution is then cooled down to 0° C. and 28 parts ofcyanuric fluoride are added dropwise, the pH decreasing and being heldat 3-4 by sprinkling in sodium bicarbonate powder. The mixture isstirred at pH 3-4 and 0° C. for 15 minutes, and a solution of the sodiumsalt of 68 parts of2,4-difluoro-5-chloro-6-(3'-amino-4'-sulfophenylamino)-pyrimidine isthen added. The solution is stirred at 20° to 25° C. and pH 5 for 5hours until no free amine is any longer detectable by diazotisationtest. The solution is used as a coupling component in dye synthesis.

To prepare the diazonium compound, 56 parts of aniline 4-β-sulfatoethylsulfone are suspended in 500 parts of ice-water, and the suspension isacidified with 45 parts of concentrated aqueous hydrochloric acid and isdiazotised with 40 parts by volume of 5N sodium nitrite solution. Themixture is stirred at about 5° C. for 2 hours and the excess nitrousacid is then destroyed by means of sulfamic acid. The diazonium saltsolution thus prepared is slowly added at pH 5.5-6.0 to the solution ofthe coupling component. The mixture is stirred for 2 hours until thecoupling has ended. pH 5.5-6.0 is maintained by adding sodiumbicarbonate. The dye is then precipitated with sodium chloride, isisolated using a suction funnel and is dried at 40° C. in vacuo.Grinding produces a red electrolyte-containing dye powder which containsthe sodium salt of the compound of the formula ##STR19## This compoundhas very good dye properties and dyes cotton and wool by the dyeing andprinting methods customary for reactive dyes in red shades having verygood wetfastness properties.

The dyes given in the following table, which dye cotton in the indicatedhue, can also be prepared analogously to the methods described.

                                      TABLE                                       __________________________________________________________________________                                                              Hue on              No.                                                                              Example                                                cotton              __________________________________________________________________________     8                                                                                ##STR20##                                             greenish                                                                      yellow               9                                                                                ##STR21##                                             bluish red          10                                                                                ##STR22##                                             bluish red          11                                                                                ##STR23##                                             bluish red          12                                                                                ##STR24##                                             red                 13                                                                                ##STR25##                                             bluish red          14                                                                                ##STR26##                                             bluish red          15                                                                                ##STR27##                                             bluish red          16                                                                                ##STR28##                                             golden yellow       17                                                                                ##STR29##                                             orange              18                                                                                ##STR30##                                             orange              19                                                                                ##STR31##                                             scarlet             20                                                                                ##STR32##                                             orange              21                                                        orange               ##STR33##                                                                    22                                                        orange               ##STR34##                                                                    23                                                        scarlet              ##STR35##                                                                    24                                                                                ##STR36##                                             yellowish red       25                                                                                ##STR37##                                             yellowish red       26                                                                                ##STR38##                                             yellowish red       27                                                                                ##STR39##                                             yellowish red       28                                                                                ##STR40##                                             red                 29                                                                                ##STR41##                                             orange              30                                                                                ##STR42##                                             scarlet             31                                                                                ##STR43##                                             orange              32                                                                                ##STR44##                                             scarlet             33                                                                                ##STR45##                                             red                 34                                                                                ##STR46##                                             scarlet             35                                                                                ##STR47##                                             bluish red          36                                                                                ##STR48##                                             red                 37                                                                                ##STR49##                                             orange              38                                                        scarlet              ##STR50##                                                                    39                                                                                ##STR51##                                             orange              40                                                        scarlet              ##STR52##                                                                    41                                                                                ##STR53##                                             red                 42                                                                                ##STR54##                                             scarlet             43                                                                                ##STR55##                                             bluish red          44                                                                                ##STR56##                                             red                 __________________________________________________________________________

Dyeing method I

2 parts of the dye obtained in Example 1 are dissolved in 400 parts ofwater; to this solution are added 1,500 parts of a solution whichcontains per litre 53 g of sodium chloride. 100 parts of a cotton fabricare introduced at 40° C. into this dyebath. After 45 minutes 100 partsof a solution which contains per litre 16 g of sodium hydroxide and 20 gof calcined sodium carbonate are added. The temperature of the dyebathis held at 40° C. for a further 45 minutes. The dyed fabric is thenrinsed, is soaped off at the boil with a nonionic detergent for aquarter of an hour, is rinsed once more and is dried.

Dyeing method II

2 parts of the reactive dye obtained in Example 1 are dissolved in 400parts of water; to this solution are added 1,500 parts of a solutionwhich contains per litre 53 g of sodium chloride. 100 parts of a cottonfabric are introduced at 35° C. into this dyebath. After 20 minutes 100parts of a solution which contains per litre 16 g of sodium hydroxideand 20 g of calcined sodium carbonate are added. The temperature of thedyebath is held at 35° C. for a further 15 minutes. The temperature isthen raised to 60° C. in the course of 20 minutes. The temperature isheld at 60° C. for a further 35 minutes. The fabric is then rinsed, issoaped off at the boil with a nonionic detergent for a quarter of anhour, is rinsed once more and is dried.

Dyeing method III

8 parts of the reactive dye obtained in Example 1 are dissolved in 400parts of water; to this solution are added 1,400 parts of a solutionwhich contains per litre 100 g of sodium sulfate. 100 parts of a cottonfabric are introduced at 25° C. into this dyebath. After 10 minutes 200parts of a solution which contains per litre 150 g of trisodiumphosphate are added. The temperature of the dyebath is then raised to60° C. in the course of 10 minutes. The temperature is held at 60° C.for a further 90 minutes. The fabric is then rinsed, is soaped off atthe boil with a nonionic detergent for a quarter of an hour, is rinsedonce more and is dried.

Dyeing method IV

4 parts of the reactive dye obtained in Example 1 are dissolved in 50parts of water; to this solution are added 50 parts of a solution whichcontains per litre 5 g of sodium hydroxide and 20 g of calcined sodiumcarbonate. The resulting solution is applied to a cotton fabric on apad-mangle in such a way that its weight increases by 70%, and thefabric is then wound onto a beam. In this state the cotton fabric isleft to stand at room temperature for 3 hours. The dyed fabric is thenrinsed, is soaped off at the boil with a nonionic detergent for aquarter of an hour, is rinsed once more and is dried.

Dyeing method V

6 parts of the reactive dye obtained in Example 1 are dissolved in 50parts of water; to this solution are added 50 parts of a solution whichcontains per litre 16 g of sodium hydroxide and 0.04 litre of sodiumsilicate. The resulting solution is applied to a cotton fabric on apad-mangle in such a way that its weight increases by 70%, and thefabric is then wound onto a beam. In this state the cotton fabric isleft at room temperature for 10 hours. The dyed fabric is then rinsed,is soaped off at the boil with a nonionic detergent for a quarter of anhour, is rinsed once more and is dried.

Dyeing method VI

2 parts of the reactive dye obtained in Example 1 are dissolved in 100parts of water in the presence of 0.5 part of sodiumm-nitrobenzenesulfonate. The resulting solution is used to impregnate acotton fabric in such a way that its weight increases by 75%, and thefabric is then dried. The fabric is then impregnated with a warmsolution at 20° C. which contains per litre 4 g of sodium hydroxide and300 g of sodium chloride, and is squeezed to a 75% weight increase andthe dyeing is steamed at 100° to 102° C. for 30 seconds, is rinsed, issoaped off at the boil with 0.3% strength solution of a nonionicdetergent for a quarter of an hour, is rinsed and is dried.

Printing method I

3 parts of the reactive dye obtained in Example 1 are sprinkled withhigh-speed stirring into 100 parts of stock thickening containing 50parts of 5% strength sodium alginate thickening, 27.8 parts of water, 20parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts ofsodium hydrogencarbonate. The print paste thus obtained is used to printa cotton fabric, which is then dried, and the resulting printed fabricis steamed at 102° C. in saturated steam for 2 minutes. The printedfabric is then rinsed, if desired soaped off at the boil and rinsed oncemore, and is then dried.

Printing method II

5 parts of the reactive dye obtained in Example 1 are sprinkled withhigh-speed stirring into 100 parts of a stock thickening containing 50parts of 5% strength sodium alginate thickening, 36.5 parts of water, 10parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 2.5 parts ofsodium hydrogencarbonate. The print paste thus obtained, whose stabilitymeets industrial requirements, is used to print a cotton fabric, whichis then dried, and the resulting printed fabric is steamed at 102° C. insaturated steam for 8 minutes. The printed fabric is then rinsed, ifdesired soaped off at the boil and rinsed once more, and is then dried.

I claim:
 1. A reactive dye of the formula ##STR57## in which D is the radical of a monoazo, metal complex azo, phthalocyanine, formazan, or dioxazine, naphthoquinone, pyrenequinone or perylenetetracarimide dye; R₁ is hydrogen or C₁₋₄ -alkyl unsubstituted or substituted by halogen, hydroxyl, cyano, C₁₋₄ -alkoxy, carboxyl or sulfo, or is methoxycarbonylmethyl, ethoxycarbonylmethyl, aminosulfonylmethyl or β-sulfatoethyl; and X is vinyl, β-sulfatoethyl, β-thiosulfatoethyl, β-chloroethyl or β-acetoxyethyl; and D is unsubstituted or substituted by alkyl having 1 to 4 carbon atoms alkoxy having 1 to 4 carbon atoms, carbacylamino having 1 to 8 carbon atoms, amino, alkylamino having 1 to 4 carbon atoms, phenylamino, N,N-di-hydroxyethylamino N,N-di-β-sulfatoethylamino, sulfobenzylamino, N,N-disulfobenzylamino, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, alkylsulfonyl having 1 to 4 carbon atoms, trifluoromethyl, nitro, cyano, halogen, carbamoyl, N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl radical, sulfamoyl, N-alkylsulfamoyl having 1 to 4 carbon atoms, N-(β-hydroxyethyl)-sulfamoyl, N,N-di-(β-hydroxyethyl)-sulfamoyl, N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo.
 2. A reactive dye according to claim 1 in which X is vinyl or β-sulfatoethyl.
 3. A reactive dye according to claim 1, in which D is a radical of the monoazo dye or metal complex azo dye.
 4. A reactive dye according to claim 3 in which X is vinyl or β-sulfatoethyl.
 5. A reactive dye according to claim 3 of the formula ##STR58## in which R₂ is hydrogen, methyl or ethyl, and the benzene ring A is not further substituted or is further substituted by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, carbacylamino having 1 to 8 carbon atoms, amino, alkylamino having 1 to 4 carbon atoms, phenylamino, N,N-di-hydroxyethylamino, N,N-di-β-sulfatoethylamino, sulfobenzylamino, N,N-disulfobenzylamino, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, alkylsulfonyl having 1 to 4 carbon atoms, trifluoromethyl, nitro, cyano, halogen, carbamoyl, N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl radical, sulfamoyl, N-alkylsulfamoyl having 1 to 4 carbon atoms, N-(β-hydroxyethyl)-sulfamoyl, N,N-di(β-hydroxyethyl)-sulfamoyl, N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo.
 6. A reactive dye according to claim 5 in which X is vinyl or β-sulfatoethyl.
 7. A reactive dye according to claim 3 of the formula ##STR59## in which the benzene ring A is not further substituted or is further substituted by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, carbacylamino having 1 to 8 carbon atoms, amino, alkylamino having 1 to 4 carbon atoms, phenylamino, N,N-di-hydroxyethylamino, N,N-di-β-sulfatoethylamino, sulfobenzylamino, N,N-disulfobenzylamino, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, alkylsulfonyl having 1 to 4 carbon atoms, trifluoromethyl, nitro, cyano, halogen, carbamoyl, N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl radical, sulfamoyl, N-alkylsulfamoyl having 1 to 4 carbon atoms, N-(β-hydroxyethyl)-sulfamoyl, N,N-di(β-hydroxyethyl)-sulfamoyl, N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo.
 8. A reactive dye according to claim 7 in which X is vinyl or β-sulfatoethyl.
 9. A reactive dye according to claim 7 in which the benzene ring A is not further substituted.
 10. A reactive dye according to claim 9 in which X is vinyl or β-sulfatoethyl.
 11. A reactive dye according to claim 3 of the formula ##STR60## in which R₃ is hydrogen, methyl or ethyl, and the benzene ring A is not further substituted or is further substituted by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, carbacylamino having 1 to 8 carbon atoms, amino, alkylamino having 1 to 4 carbon atoms, phenylamino, N,N-di-hydroxyethylamino, N,N-di-β-sulfatoethylamino, sulfobenzylamino, N,N-disulfobenzylamino, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, alkylsulfonyl having 1 to 4 carbon atoms, trifluoromethyl, nitro, cyano, halogen, carbamoyl, N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl radical, sulfamoyl, N-alkylsulfamoyl having 1 to 4 carbon atoms, N-(β-hydroxyethyl)-sulfamoyl, N,N-di(β-hydroxyethyl)-sulfamoyl, N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo.
 12. A reactive dye according to claim 11 in which X is vinyl or β-sulfatoethyl.
 13. A reactive dye according to claim 3 of the formula ##STR61## in which the benzene ring A is not further substituted or is further substituted by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, carbacylamino having 1 to 8 carbon atoms, amino, alkylamino having 1 to 4 carbon atoms, phenylamino, N,N-di-hydroxyethylamino, N,N-di-β-sulfatoethylamino, sulfobenzylamino, N,N-disulfobenzylamino, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, alkylsulfonyl having 1 to 4 carbon atoms, trifluoromethyl, nitro, cyano, halogen, carbamoyl, N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl radical, sulfamoyl, N-alkylsulfamoyl having 1 to 4 carbon atoms, N-(β-hydroxyethyl)-sulfamoyl, N,N-di(β-hydroxyethyl)-sulfamoyl, N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo.
 14. A reactive dye according to claim 13 in which X is vinyl or β-sulfatoethyl. 